Synthesis of vinylidene epoxides from allylic sulfonium salts



United States Patent Ofice US. Cl. 260-348 7 Claims ABSTRACT OF THE DISCLOSURE Reaction of an allylic sulfonium salt 1) with an aldehyde free of ot-hydrogen (2) in the presence of a strong aqueous base provides a novel synthesis of vinylidene epoxides (3), e.g.:

The vinylepoxides, such as butadienemonoxide, are useful polyfunctional monomers such as scavengers for hydrogen halide.

This is a continuation-in-part of application Ser. No. 502,365 filed on Oct. 22, 1965 by Melvin I. Hatch, Patent No. 3,426,046, issued Feb. 4, 1969.

BACKGROUND The formation of alkyl sulfonium ylides from sulfonium salts in a strongly basic, non-aqueous solution is known. For example, dimethylsulfonaum methylide is formed by reaction of trimethylsulfonium iodide with methylsulfinylcarbanion is dimethylsulfoxide. Such sulfonium ylides can react in the non-aqueous solution with carbonyl compounds to form epoxides. [Corey & Chaykovisky, I. Am. Chem. Soc., 84, 3782 (1962); Franzen & Driessen, Tetrahedron Letters, 661 (1962), Ber., 96, 1881 (1964).] However a similar reaction in aqueous solution has not been described, even though it would have numerous advantages for industrial practice.

STATEMENT OF THE INVENTION It has now been discovered that allylic sulfonium salts react in strongly alkaline aqueous solutions with an aldehyde free of u-hydrogen to form vinylidene epoxides. More specifically a process has been discovered for preparing vinylidene epoxides by reacting in aqueous solution: (1) an allylic sulfonium salt of the formula:

where R is H or a C -C alkyl group, R and R are independently C -C alkyl or hydroxyalkyl groups, and X is a counteranion,

(2) an aldehyde, RCHO, free of tit-hydrogen and (3) a water-soluble base having a pK greater than 11.0 to form (4) a vinylidene epoxide of the formula:

3,462,462 Patented Aug. 19, 1969 In a preferred embodiment the allylic sulfonium salt and aldehyde are reacted with base in a heterogeneous mixture of water and a water-insoluble organic extractant which removes the vinylidene epoxide from the aqueous phase as it forms.

By this process aldehydes can be converted into useful vinylidene epoxides, compounds often difficult to prepare by other methods. Not only can these epoxides be used to scavenge HCl or HBr or to stabilize a chlorinated solvent as shown by Dial US. Patent 3,025,331, but also as a polyfunctional monomer useful in copolymerizing with alkylene oxides as shown by Bailey US. Patent 3,031,439 or in the synthesis of new organosilicons described by Plueddemann US. Patent 3,120,546.

Reactants.Essential is an allylic sulfonium salt of the formula:

where R is H or a C -C alkyl group, R and R are independently C -C alkyl or hydroxyalkyl groups, and X is a counteranion. Such sulfonium salts can be prepared by known reactions. For example, allyl and methallyl sulfonium salts are obtained by reaction of allyl or methallyl chloride with dimethyl sulfide or bis(2-hydroxy= ethyl) sulfide.

Normally the allylic sulfonium salts have a halide counteranion (X). However, the halide salt can be converted into other anionic salts such as the carbonate, nitrate, sulfate, acetate, perchlorate or tosylate salt by conventional ion exchange techniques when desired.

The process is eifectively limited to the condensation of allylic snlfonium salts with aldehydes free of a-hydrogen (2) because of competing reactions. Formaldehyde, furfural, benzaldehyde, p-terephthaldehyde, and other C -C aromatic aldehydes are particularly suitable. The aldehyde can contain more than one reactive carbonyl group as well as alkyl, halo, hydroxyl, alkoxyl and similar substituent groups which do not interfere with the desired epoxidation.

The process also requires a strong water-soluble base. (3) The base should have a water solubility of at least 0.1 weight percent and a pK in aqueous solution of at least 11.0. Sodium hydroxide is preferred, but other strong alkaline and alkaline earth metal bases such as potassium hydroxide, lithium hydroxide, calcium hydroxide or calcium oxide can be used.

Reaction conditions.Water is an effective solvent for the allylic sufonium salts. Indeed the sulfonium salts are often prepared in aqueous solution and such solutions can be used in the present process without isolation of the sulfonium salt. At times addition of a moderate amount of a water-soluble C -C alcohol, such as methanol, isopropanol, ethylene glycol, Z-ethoxyethanol, or 1,4-butanediol, is advantageous to increase the mutual solubility of the reactants.

In a preferred process, a water-insoluble organic extractant is added to remove the epoxide from the aqueous phase as it is formed, thereby minimizing hydrolysis and other reactions. To facilitate recovery of the extracted epoxide, an extractant with a boiling point between 30 C. and C. is often used. Particularly suitable are aliphatic and aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, toluene, and ethylbenzene as well as kerosene and petroleum naphtha, C -C chlorinated hydrocarbons which are stable to aqueous alkali under reaction conditions also are effective extractants. Typical are methylene chloride, carbon tetrachloride, methylchloroform, 1,2-dichloroethane and 1,2- dichloropropane.

At times with a less reactive epoxide and carefully controlled conditions, good yields can be obtained without an 3 4 extractant. Low boiling epoxides can occasionally be dis- (C) Table I summarizes data from similar runs made tilled directly out of the aqueous phase. But, in general, with 1.24.5 N aqueous allyldimethylsulfonium chloride. use of a water-insoluble extractant is preferred. In some instances the initial sulfonium chloride was pre- At least one mole of base is required per mole of sulpared in methanol or isopropanol rather than water and fonium salt. Generally a moderate excess of base, eg, the aqueous alcohol was used as the epoxidation medium.

about 1.2-5.0 moles of base per mole of sulfonium salt, The yields of epoxybutene and propylene oxide given in is desirable. Also, for good yields of the vinylidene epOX- Table I are based on gas chromatographic analysis of the ide, a slight excess of aldehyde is preferred. recovered organic phase.

TABLE L-SYNTl-IESIS OF BA-E POXY-4IHENYL-1-BUTENE Percent yield Mole Ratio 'I. 0. Epoxylropylono Run o CHO/S+ NaOH/S Extractanl; Initial butono oxido 1.0 1.6 Benzene 35 37 21 1.0 1.6 35 4s is 3.0 1.4 40 57 13 1.0 2.5 35 4s 1a 1.0 1.6 5 35 0 so 1 1.0 1.4 Perchloroethylene... 25 28 1.0 1.3 None 25 63 1-2 1.0 1.6 .do 35 73 1 1 By gas chromatographic analysis based on initial sulfonium salt. 2 Run in aqueous alcohol.

Optimum conditions for a given epoxidation will depend Example 2Butadienemonoxide.To a stirred mixture upon the reactivity and stability of the reactants and prod- 25 of 1.0 mole of 4.5 N aqueous allyldimcthylsulfonium ucts. For example, decreasing the rat of competing basechloride, 3.0 mole of 30% formaldehyde and about an catalyzed reactions of the aldehyde generally favors epoxequal volume of toluene at 45 C. was added 1.35 mole of idation. Also the yield of vinylidene epoxide is greatly in- 50% NaOH in 3 portions, A vigorous reaction occurred fluenced by the reaction temperature and aldehyde concenwith a temperature rise to 70 C. After 10 minutes reflux tration. The allylic sulfonium salts react readily in aque u 30 at 70 C., the mixture was cooled and the organic phase alkali at temperatures of about 100 C. Substantially recovered. By analysis a yield of mixed epoxides complete reaction is often achieved in 0.1-2 hours at was found based on initial sulfonium salt. Distillation, 80 C. However, a lower reaction temperature, e.g., 5- chromatographic and infrared analyses indicated an 8% 60 C., and a high concentration of sulfonium salt and yield of 3,4-epoxy-1-butene (butadienemonoxide) and a aldehyde favor the formation of the vinylidene epoxide. 12% yield of propylene oxide.

At higher temperatures and in dilute solution a competing E l 3 4-fnrf r l-3,4- o .1.b A i t hydrolytic rearrangement of the allylic sulfonium salt t of 0.30 mole of allyldimethylsulfonium chloride and 0.30 an alkylene oxide occurs at a significant rate. mole of 2-furfural in water and benzene was stirred and Within the general scope of the disclosed process, 0P- heated to about 35 C. Then 0.47 mole of 50% NaOH timum reaction conditions for a given epoxidation can be was added. After 15 minutes at reflux, the mixture was determined in a routine manner. When necessary a m derquenched and the light brown organic phase was separated. ate pressure can be used to maintain a liquid phase and After stripping dimethyl sulfide and benzene, the liquid minimize the loss of volatile materials. residue was distilled in vacuo. A 69% yield of liquid 4- To illustrate further the present invention the following furf 1-3,4- oxy-l-butene, B.P. 5153 C./ 3 mm. was examples are given. Unless otherwise specified, all pa t obtained. The epoxide had a minimum purity of 92% by and percentages are by weight. epoxide analysis.

Example 13,4-epoxy-4-phenyl-1-butene.-(A) A miX- Example 44 phenyl-3,4-epoxy-2-methyl-1-butene.A

t f 282 parts mole) of allyl chl d 255 Parts mixture of 0.15 mole of 4.3 N aqueous methallyldimethylmole) of dimethyl Sulfide and 300 Parts f Water sulfonium chloride, 0.15 mole of benzaldehyde, 0.24 mole Were Stirred at room temperature for 8 y The aqueous of NaOH and about an equal volume of benzene was phase was separated and purged with nitrogen to remove 50 h d at r flux (63-65 C.) for 1.5 hrs. The organic residual dimethyl sulfide y analysis it Was N in phase was separated, neutralized, and then the volatile niafonium Chl r d With an 89% Conversion 0 allyldimethyl' terial was stripped by distillation. The overhead distillate sulfonium chloride and less than 1% hydrolysis. contained a 12% yield of isobutylene oxide while the resi- (B) T0 a StlIl'Cd mixture Of 0.30 111016 Of the aqueous due contained a 57% yield of 4-phenyl-3,4-cp Xy-2- allyldimethylsulfonium chloride solution, 0.30 mole of 5a methypl.butenebenzaldehyde and about an equal volume of toluene at I claim; 30 C. was rapidly added 0.45 mole of 30% sodium hy- 1 A process for preparing vinylidene epoxides which droxide. An exothermic reaction occurred with a temperacomprises; reacting in aqueous solution ture rise to about 60 C. After about 15 minutes at 60 1 an allylic lfo j Salt of the f l C., the organic phase was separated. 60

An epoxide analysis of the recovered organic phase by R the pyridine-HCl method indicated a 58% yield of epoxides based on the initial sulfonium salt. Infrared and 2= 2 iR2X- chromatographic analysis established the presence of both propylene oxide (21%) and 3,4-epoxy-4-phenyl-l-butene 65 where (37%). Fractional distillation gave a 35% yield of a liquid, 3,4-epoxy-4-phenyl-l-butene with a minimum purity of 85% by epoxy and olefinic function group analyses. h d 11 d d Nuclear ma netic resonances ectra oft e isti e ro net indicated t hat it contained about 40% cisand 60% A aldehyde, R'CHO, selected from the group trans-epoxide. Mass spectra data were consistent with this slstlng formaldehyde, z'furfllfal, and a s- 12 isomer distribution. Analysis of the distillation fractions alomatlc aldehyde, and boiling below 65 C. confirmed the presence of about 20% (3) a water-soluble base having a pK greater than propylene oxide. 11.0 to form R is H or a C -C alkyl group,

R and R are independently C C alkyl or hydroxyalkyl groups, and

X is a counteranion,

5 6 (4) a vinylidene epoxide of the formula: 6. The process of claim 4 where the vinylidene epoxide is 3,4-epoxy-l-phenyl-l-butene. j: 7. The process of claim 4 where the vinylidene epoxide CH OHCHR is butadienemonoxide.

h The process of claim 1 where the base is sodium 5 R f r e Cited y roxl e.

3. The process of claim 1 Where a water-insoluble or- Corey et 10111" Amer Chem 84 (1962) ganic extractant is added to the reaction mixture to remove 3782' the epoxide from the aqueous phase as it is formed. Franzen et Tetrahedron Lettars (1962) 4. The process of claim 3 wherein the extractant is 0 Franzen at Deutchem- P- 1831- a hydrocarbon or a C C chlorinated hydrocarbon said v extractant having a boiling point between about 30 NORMA MILESTONE Pumary Exammer 130 C.

5. The process of claim 4 wherein the sulfonium salt is allyldimethylsulfonium chloride. 15 609 

